High energy food supplements comprising linear aliphatic 1,3-diols

ABSTRACT

Metabolic energy sources in foods are increased by incorporating in the foods from 1 to 75 percent by wt. of a compound selected from linear aliphatic polyols an mixtures thereof. The polyols have from about five to 15 carbon atoms in the chain and hydroxy groups only on alternate carbon atoms and on at least the first and third carbon atom.

United States Patent [191 Frankenfeld et a1.

HIGH ENERGY FOOD SUPPLEIVIENTS COMPRISING LINEAR ALIPHATIC [56]References Cited 13-91015 UNITED STATES PATENTS Inventors: John W.Frankenfeld, Atlantic 3,667,965 6/1972 Frankenfeld et a1 99/150 RHighlands, N.J.; Sanford A. Miller, 3,732,112 /1973 Frankenfeld et .211.Chestnut Hill, Mass, 2,901,31 l 8/1959 Nusslein et aI.

2,681,878 6/1954 Kauppi Asslgneer E580 Research and Englneel'lng2,904,436 9/1959 Auerbach 99/3 Company, Linden, NJ.

d; June 197 Primary Examiner-N0rman Yudkoff Appl. No.: 268,089

Assistant Examiner-Curtis P. Ribando Attorney, Agent, or Firm-LeonChasan Related US. Application Data Continuation-impart of sci. No.809,645, March 24, 1969, which is a continuation-in-part of Ser. No.725,782, Feb. I, 1968.

US. Cl.

Int. Cl Field of Search99/2 R, 2 M, 2 G, 3, 2 F, 2 NO,

99/ 150 R A231: l/00 and third carbon atom.

99/2 N, 4, 122, 123, P, 91, 92, R,

AVE. CHANGE IN BODY WEIGHTS (IO RATS) gms.

3o GROWTH CURVES FOR TEST ANIMALS WITH VARIOUS DIETARY ENERGY SOURCES(SECOND WEEK OF TWO WEEK TEST) AMOUNT OF HIGH ENERGY SUPPLEMENT (grns) lT CONTAIN l8/ CASEIN AS A PROTEIN SOURCE PLUS SIEFF ICIENT VITAMINS ANDMINERALS TO MAINTAIN GOOD GROWTH ABSTRACT Metabolic energy sources infoods are increased by incorporating in the foods from 1 to 75 percentby wt. of a compound selected from linear aliphatic polyols an mixturesthereof. The polyols have from about five to 15 carbon atoms in thechain and hydroxy groups only on alternate carbon atoms and on at leastthe first 9 Claims, 1 Drawing Figure [451 Feb. 12, 1974 AVE. CHANGE INBODY WEIGHTS (IO RATS) gms.

PATENTED FEB 12 I914 3791. 241

GROWTH cuRvEs FOR TEST ANIMALS WITH VARIOUS DIETARY ENERGY SOURCES(SECOND WEEK OF Two WEEK TEST) I I l AMOUNT OF HIGH ENERGY SUPPLEMENT(gms) DIETS CONTAIN I8% CASEIN AS A PROTEIN SOURCE PLUS SUFFICIENTVITAMINS AND MINERALS TO MAINTAIN GOOD GROWTH HIGH ENERGY FOODSUPPLEMENTS COMPRISING LINEAR ALIPHATIC 1,3-DIOLS CROSS REFERENCETOYRELATED APPLICATION This application is a Continuation-in-Part of US.Ser No. 809,645, filed Mar. 24, 1969, which in turn is aContinuation-in-Part of U.S.,Ser. No. 725,782, filed May 1, 1968.

BACKGROUND OF THE INVENTION The present invention relates generally tohigh energy food compositions. More specifically, the present inventionrelates to a method of supplementing natural and/or compounded human andanimal foods with materials that provide increased metabolic energysources. The suitability of various classes of compounded foods foranimals and humans depends upon the skill and integrity used in theirprocessing. There is no best food that can be prepared to meet allexisting conditions, and the ingredients in a mixed feed may be variedconsiderably. However, compounded foods must be sold on the basis ofguaranteed minimum protein, fat, and nitrogen-free extract contents, andguaranteed maximum crude fiber and ash contents. The fat content ofcompounded foods is further limited in that the presence of natural fatsand oils in these foods tends to promote their deterioration. Thus, inmany instances, compounded foods are deficient in that they do notcontain sufficient amounts of fats and natural oils or other energyproducing elements.

Unfortunately, not only diets based on compounded foods tend to beunbalanced nutritionally but it is well known that in many countries ofthe world a sufficient variety of natural foods are not available toprovide adequate diets for humans. Thus,.there is a need forsupplementing natural foods with additional energy sources where thetotal diet may well be deficient or where some other special reasonsexist.

SUMMARY OF THE INVENTION According to the present invention a method forincreasing the metabolic energy sources of natural and compounded foodsdesigned for human or animal consumption comprises incorporating inthose foods from 1 to 75 wt. percent on a dry basis of a linearaliphatic polyol having from five to fifteen carbon atoms and hydroxygroups only on alternate carbon atoms and on at least the first andthird carbon atom. Preferably, the metabolic energy sources of human oranimal foods are increased according to this invention by incorporatingin these foods from to above wt. percent of a linear aliphatic diolhaving from five to 10 carbon atoms in the molecule and having thehydroxy groups on the first and third carbon atom. Optionally mixturesof such polyols may be incorporated in the amounts specified.

In one embodiment of the present invention novel high energy foodcompositions are provided comprising food designed to be consumed byhumans or animals and from I to 75 wt. of a dihydroxy substituted linearaliphatic hydrocarbon or mixtures thereof, the said hydrocarbon havingfrom five to 15 carbon atoms and having the hydroxy groups on the firstand third carbon atom. Preferably, the high energy food compositionsdesigned for animal consumption constitute a basal diet in an amountsufficient to support normal growth and the specific polyols furtherdescribed herein.

BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a graph illustrating thebeneficial results provided in incorporating, in accordance with thisinvention, specific polyols in foods whereby the metabolic energy sourceof the foods are increased.

DETAILED DESCRIPTION OF THE INVENTION The invention is based on thediscovery that if particular polyols are used as additives in foods anexcellent, high quality, high energy product results. These aliphaticpolyols, such as aliphatic 1,3-diols and 1,3,5, xpolyols of five carbonatoms or more are nontoxic, energy-dense compounds which are veryexcellent when utilized for the production of energy. These compoundsalso have additional advantages over traditional caloric sources, suchas fats and carbohydrates, and may be used to replace fats andcarbohydrates in human and animal diets.

These aliphatic 1,3-diols and 1,3,5, x-polyols provide excellent sourcesof metabolic energy for humans and animals. These materials aresynthesized easily, they have desirable properties, and are readilymetabolized. These materials have several advantages over usual energysources in that they are higher in caloric density than carbohydratesand proteins and are more stable than fats and thus may be used asreplacements for natural foods. These materials are colorless, virtuallyodorless and tasteless and are easily formulated into human or animalfoods or feeds. Since they are produced by chemical means from readilyobtainable starting materials, the 1,3-diols and 1,3,5, x-polyols havemarketing advantages in that they are available at stable prices and andin consistent quantities. They also may be produced readily inlocalities where arable land for grazing or cultivation is scarce.

The particular polyols of the present invention are linear aliphaticpolyols, i.e., they are hydroxy substituted normal paraffins whichcontain from about five to 15 carbon atoms in the molecule, preferablyabout five to 10 carbon atoms in the molecule. Polyols con taining lessthan five carbons are too low in calories to have any advantage overnatural foods. The polyols contain hydroxy groups only on alternatecarbon atoms and at least on the first and third carbon atom. It is this1,3-dihydroxy or 1,3,5 x-poly-hydroxy configuration which renders thesecompounds useful as foods and food additives. Polyalcohols with hydroxylgroups in other positions on the carbon chain are not useful as foods asis shown in the specifications below. In addition to being non-toxic andreadily metabolized the 1,3- diols and 1,3,5 x-polyols claimed hereinhave certain other advantages making them highly desirable as foods andfood additives: (1) they are stable, non volatile oils and have a longstorage and shelf life; (2) they have an appreciable water solubilityand are readily emulsified making them easy to formulate in foodpreparations; (3) they are readily adsorbed in the intestinal tract; and(4) they have a high calorie density, i.e., they afford a large numberof calories on being metabolized for a given weight or volume of thecompound. A summary of the compounds specifically claimed in thisinvention along with their caloric densities and some of their physicalproperties, is presented in Table l.

TABLE 1 some POLYOLS AND THEIR PHYSICAL PROPERTIES Calorie Density KcaL/gm' Diol BP/mm(C) Taste. Odor, ctc.

1,3-penlanedinl l,3-hexanediol 8l82/0.2 7.8

l,3-heptanediol 90/0.5 8.2

1,3-octanediol 8789/0.3 8.5

1,3-nonanediol l26ll.l 8.7

1,3-decanediol mp =303l 8.9

1,3-undecanediol mp=41-42 9.1

1,3.5-hexanetriol ll32/0.2

It is apparent from the above data that the 1,3-diols and 1,3,5x-polyols are energy dense compounds with desirable physical properties.Of the common foods (protein: 4.1 Kcal/gm; carbohydrate: 4.1 Kcal/gm;and 3 fat: 9.3 Kcal/gm.) only fats have caloric densities comparable tothese polyalcohols. Fats, however, have severe limitations as energysources because they tend to produce undesirable ketone bodies in theblood when present at high levels in the diet. A practical upper limitof about 50 percent of total calories can be tolerated in the form offats.

All compounds listed in Table I are viscous, nonvolatile oils. Theseproperties render them stable and easy to incorporate into human oranimal diets. For these reasons as well as those enumerated in theforegoing, 1,3-diols and 1,3,5 ,x-polyols are superior energy sourceswhich can serve as replacements for carbohydrates or fats in human andanimal diets.

While these materials may be prepared by any satisfactory method thefollowing methods are very satisfactory for their preparation.

The Reformatsky reaction followed by reduction:

Zn RCHO BrCH COIOiEB H or noncmcmcm, RoHcHIoH, H Hydride H Llt a, .7 V.RCH=CH HCHO RCHCH CH;

The l ,3,5 -lieitanetriol has been synthesized by the following sequenceof reactions:

Clh=CIIClIICIhOH CIIQCIIO CHICHiCHCHiCHCHI COCH:

OCOCHI OCOCH:

In o I ori Other l,3,5,x-polyols (polyvinyl alcohols) of mediummolecular weight may also be obtained by selective po- Mg XCHaCHO CHJCred H omen cmoHo CHaCH 15 lymerization of acetaldehyde followed byreduction:

As pointed out heretofore, the compounds of the present invention arefood supplements and may be incorporated in animal and human foods suchas in cereals, meal, and any food compound designed for human or animalconsumption. They may be used in any application in which fats andcarbohydrates are currently used. The amount of these polyols used mayvary from lpercent of the dry weight of the diet. Preferably, to getoptimum utilization, they should be used in amounts ranging between l020percent of the dry weight of the diet.

Compounded foods include formulations of natural foods such ascombinations of grains, soybeans and the like as well as prepared foodssuch as bread, the socalled breakfast cereals, formula diets, andsynthetic milks.

Two illustrations of feed formulations that may be supplemented with the1,3 diols and 1,3,5-x-polyols of this invention are given in Tables 11and Ill below.

TABLE ll ALL MASH STARTING FEED FOR CHlCKENS Ingredient Pounds perPounds per ton pounds Ground yellow corn 25.00 500 Pulverized oats 15.00300 Wheat middlings, standard 15.00 300 Soybean meal 12.50 250 Corngluten meal 9.75 195 Fish meal 8.50 170 Dried skim milk 250 50Dehydrated alfalfa meal 7.50 Dried distillers solubles 2.50 50 Mineralmixture No. l 1.30 26 Salt 0.30 6 Feeding oil (1000 A, 400 D) 0.15 3Total 100.00 2000 TABLE 111 FISH FORMULAE Commercial Ration Wt. RangeWheat Middlings 25 10-30 Fish Meal 25 10-30 Cottonseed Meal 20 10-30Meat Meal 5 l-9 Liver Meal 5 l-9 Brewer's Yeast 5 l-9 Distillers Source4 l-7 Dried Skim Milk 3 0.5-5.0 Blood Meal 3 0.5-4.0 Salt 2 0.5-4.0

TABLE III -Continued FISH FORMULAE Commercial Ration Wt. Range AlfalfaMeal 1.3 0.52.05 Vitamins 1.7 0.53.0

Wt. Soy Protein 7.59 Skimmed Milk 9.40 Dextrose-Maltose 0.86 Corn Oil3.85 Lemon Juice (or other flavoring 1.00 material) Water 77.30 Salt qsVitamins and Minerals qs In order to further illustrate the invention,various tests were carried out which are illustrated in Tables V and VI. It is apparent from these data that the positioning of the hydroxylgroups has a significant effect on the toxicity of these compounds andon their ability to be metabolized. Having hydroxyl groups on the firstand third carbons of the chain is sufficient to reduce the toxicity andrender the compounds metabolizable.

LD values are a common measure of the toxicity of a compound. Theyrepresent the lethal dose for a 50 percent kill of the animals testedper unit weight of the animals. The higher the LB the lower thetoxicity. The data in Table V establish that the 1,3 and especially thel,3,5,xconfiguration of polyalcohols are the least toxic. The LD valuesare significantly higher in compounds possessing this structuralfeature. The LD values given in Table V were obtained by giving testanimals graded single dosesof the test compounds orally and observingthem for 1 week.- The number of deaths in each group was noted and thedose .required for a 50 percent kill taken as the LD value. In manycases no death occurred, even at the 20 mllkg level (about as much asyou can give a rat in one dose), hence the 20" values shown in thetable.

TABLE V ACUTE TOXlClTY 0F VARlOUS POLYOLS Single dose in rats 'LD IethuIdose for 50% kill The data shown here show the advantage of the 1,3-dihydroxy and l,3,5,x-polyhydroxy structures in reducing toxicity ofpolyols. Compare compound 1 with 2,

for example, and compounds 5 and 6 with compound 3. The only exceptionis 1,5-hexanediol (compound 4) which is not toxic. However, it is notwell metabolized. (See Table VI.)

TABLE VI NUTRITIONAL TESTING OF DlOLS AND POLYQLS' Available Calories Kcal/gm) Compound Calc. Obs, Utilizetl 1,3-pentanediol 7.5 7.8 100l.3-heptanediol 8.2 8.0 98 1,3,5-hexanetriol 6.6 3.0 45 1,3-hexanediol7.8 6.6 l,3-octanediol 8.2 5.8 71 1,5-hexanedio1 7.8 0.0

Values given are averages of several experiments Determined by dividingobserved calories by calculated calories JBased upon amount of testcompound consumed; the test animals ate less of the 1,3,S-hexanetriol.What was eaten was metabolized to the extent of 45% Rats experienced aweight loss with this compound The data in Table VI clearly establishthe usefulness of 1,3-cliols and 1,3,5,x-polyols as metabolic energysources. In nearly all instances these compounds were 70 percentutilized or better. In certain cases the utilization was 100 percent.The test compounds were fed successfully at levels up to 70 percent ofthe dry weight of the diet. However, they were somewhat better toleratedby the animals at levels of 525 percent (dry weight). The poor resultsobtained with 1,5-hexanediol further confirms the importance of the 1,3-or 1,3,5, positioning of the hydroxyl groups. Compounds with hydroxylson other positions are not metabolized satisfactorily. There was noobserved reduction in utilization with increasing molecule weight of theseries of diols. In fact, the higher molecular weight compounds may bemore valuable since they possess a higher caloric density.

The usefulness of these polyols is further demonstrated by the typicalgrowth curves shown in FIG. 1. These curves were obtained by feedingtest groups, of 5-10 rats each, various amounts of several high energysupplements. The basal diets in each case contained sufficient protein,salts, vitamins and minerals to support normal growth. However, thebasal diets were deficient in energy (calories). This deficit was, inpart, overcome by adding varying amounts of several energy sources. Thegreater the amount of energy, the better the growth of the animals. Thisis evidenced by the consistent, positive slope of the lines in FIG. 1.

The curves in FIG. 1 were obtained by plotting the average change inbody weight of the test animals against the amount of high energysupplement added to the basal diet. Curves 1 and 2 were obtained withglucose and sucrose, two typical, natural foods of the carbohydratetype. Curve 5 was obtained with lard, a typical, natural fat. Curves 3and 4 represent two of the compounds claimed in this invention,1,3-hexanediol and 1,3-octanediol. Similar curves were obtained with allthe 1,3-diols listed in Table VI. The growth obtained with lard (curve5) is considerably better than that from the carbohydrates (curves 1 and2) which is to be expected since lard provides twice the amount ofcalories per unit weight than does glucose or sucrose.

These data clearly indicate the value of the 1,3-diols as dietary energysources. These compounds are manifestly superior to the carbohydratesand are virtually as good as lard. In addition, they possess all theadvantages over natural foods which were enumerated above.

The feeding studies were conducted ad libitum, that is, the animals weregiven free choice as to food intake. The good results shown in FIG. 1indicate that there is no palatability problem; the animals readilyaccepted the new diets. Thus, the data in Table 1 show the diols arepotentially high in energy (calories) and possess certain desirablephysical properties. The data in Table V establish the fact that the1,3-diols and l,3,5,xpolyols are nontoxic and, by comparison with otherdi- 01s, that the 1,3- and l,3,5,x-configuration uniquely reduces thetoxicity of polyalcohols. The data in Table V1 indicate that the1,3-diols and l,3,5,x-po1yo1s are metabolized well while other diols,such as the 1,5- hexanediol, are not. This further implies that thediols are readily absorbed and are palatable to the animals.

The data in FIG. I extend those in Table V1 and make a direct comparisonwith traditional foods (such as fats and carbohydrates) possible. It isapparent that the 1,3-diols are better than carbohydrates and equal to,or better, than fats. Therefore, they (the diols) may be used asreplacements for fats and carbohydrates.

LEGEND FOR FIGURE 1 fat The food formulations of the present inventionare particularly desirable in commercial fish feeds. Fish farming is arapidly expanding industry which provides one important method forproducing good quality protein for human consumption. This industryrequires the development of new, synthetic feed formulations containingthe necessary nutrients in the proper form and consistency for optimumgrowth of the fish under artificial conditions. The 1,3-diols areparticularly useful as an energy-yielding component of the fish diet forthe following reasons.

1. They are high in energy (calories); they are nontoxic; they aremetabolized completely.

2. They can be produced readily by chemical means and reduce thedependence of the fish industry on agricultural nutrients.

3. They act as mold inhibitors and preservatives for the diets.

4. They are viscous oils of intermediate water solubility and goodsurface active properties so that they can serve as a binder and aplasticizer to give the formulations the proper consistency andstability.

The properties mentioned in (4) are especially important. They give1,3-diols a significant advantage over other energy sources. A majorproblem in feeding aquatic animals is molding the diet into a suitableform, such as a pellet, which will be stable under aqueous conditions.The proper consistency for such formulations varies with the type ofanimals being fed. This is especially critical in feeding shell fishwhich will not ingest the food unless it has just the right consistency.The 1,3-diols have physical properties rendering them uniquely useful asa binder and plasticizer for these formulations.

A typical commercial fish feed formulation as modified according to thisinvention is shown in Table V11.

Any one of the diols or a mixture of same may be used. The diols may beincorporated in the ration at levels from l-20 percent, preferably from5-15 percent and, most preferably, about 10 percent. 1f higher levelsare desired, the diol should replace an equal amount of wheat middlingsor cottonseed meal or both.

The diets may be blended and extruded into small pellets or into othersuitable forms, depending on the particular application. Many types offish can be raised. Examples are trout, salmon, bass, perch, catfish,carp, sardines, mackerel, the Asian milkfish, mullet and others. Manyshell fish, mollusks, lobsters, oysters and shrimp are also candidatesfor this type of aquaculture.

Similarly, the mash feed shown in Table 11 is modified, for example, bybacking out 5 lbs. of the 25 lbs. of ground corn and adding in lieuthereof, 5 lbs. of 1,3- heptanediol. Other diols, or mixtures of diols,can be incorporated in the mash at levels ranging from 1 to 20 percent.

A typical high energy bread formula is shown in Table VIII. The formulais baked in the normal manner using the sponge method of baking.

TABLE V111 HIGH ENERGY BREAD FORMULA CONTAINING 1,3-D10LS Weight (grams)Flour 7000 Water 430.5 Yeast 14.0 Yeast food 3.5 Non-fat milk solids21.0 Sugar 35.0 1,3-Diol 5.0 Card 12.0 Salt l4 0 What is claimed is:

1. A method of increasing the metabolic energy sources in human andanimal basal diets comprising incorporating in said basal diets fromabout 10 percent to 20 percent on a dry weight basis of a compoundselected from linear aliphatic 1,3-diols and mixtures thereof, saiddiols having from five to 15 carbon atoms in the molecule.

2. The method of claim 1 wherein the diol has from five to 10 carbonatoms.

3. The method of claim 1 wherein said diol is 1,3- hexanediol.

4. in basal diets designed for human consumption that contain sufficientprotein, salts, vitamins and minerals to support normal growth, theimprovement comprising incorporating in said basal diets from 10 percentto 20 percent on a dry weight basis of a compound selected from linearaliphatic diols and mixtures of diols, said diols having from five to IDcarbon atoms and having hydroxy groups on the first and third carbonatoms whereby the metabolic energy sources of the diets are increased. 7

5. A method for increasing metabolic energy sources in animal basaldiets comprising incorporating in said diets from about 1 percent toabout 20 percent by weight of a compound selected from the linearaliphatic diols having from five to carbon atoms in a molecule beingfurther characterized by having hydroxy groups only on the first andthird carbon atom.

. 6. A high energy food composition comprising a basal animal dietcontaining sufficient protein, salts, vitamins and minerals to supportnormal growth and from 1 percent to 20 percent on a dry weight basis ofa linear aliphatic diol, said diol having from five to 15 carbon atomsand having hydroxy groups on the first and third carbon atoms.

7. The composition of claim 6 wherein said diol is 1,3-heptanediol.

8. A high energy fish food composition comprising a basal fish diet inamounts sufficient to support normal growth and from about 5 to about 15percent of a linear aliphatic diol having from five to 15 carbon atomsand having hydroxy groups on the first and third carbon atom.

9. The composition of claim 8 wherein said diol is 1,3-heptanediol.

2. The method of claim 1 wherein the diol has from five to 10 carbonatoms.
 3. The method of claim 1 wherein said diol is 1,3-hexanediol. 4.In basal diets designed for human consumption that contain sufficientprotein, salts, vitamins and minerals to support normal growth, theimprovement comprising incorporating in said basal diets from 10 percentto 20 percent on a dry weight basis of a compound selected from linearaliphatic diols and mixtures of diols, said diols having from five to 10carbon atoms and having hydroxy groups on the first and third carbonatoms whereby the metabolic energy sources of the diets are increased.5. A method for increasing metabolic energy sources in animal basaldiets comprising incorporating in said diets from about 1 percent toabout 20 percent by weight of a compound selected from the linearaliphatic diols having from five to 15 carbon atoms in a molecule beingfurther characterized by having hydroxy groups only on the first andthird carbon atom.
 6. A high energy food composition comprising a basalanimal diet containing sufficient protein, salts, vitamins and mineralsto support normal growth and from 1 percent to 20 percent on a dryweight basis of a linear aliphatic diol, said diol having from five to15 carbon atoms and having hydroxy groups on the first and third carbonatoms.
 7. The composition of claim 6 wherein said diol is1,3-heptanediol.
 8. A high energy fish food composition comprising abasal fish diet in amounts sufficient to support normal growth and fromabout 5 to about 15 percent of a linear aliphatic diol having from fiveto 15 carbon atoms and having hydroxy groups on the first and thirdcarbon atom.
 9. The composition of claim 8 wherein said diol is1,3-heptanediol.